Cp*W(NO)(CH2CMe3)(2) (1) and Cp*W(NO)(CH2SiMe3)(eta(2)-CPhCH2) (2), two complexes which initiate the catalytic ring-retaining oligomerization of cyclic olefin substrates from cyclopentene to cyclooctene, have been reacted with analogous heteroatom-containing cyclic olefins under thermolytic conditions. These reactions with 2,5-dihydrofuran, 3,4-dihydro-2H-pyran, and 1,2,3,6-tetrahydropyridine do not result in the formation of oligomeric organic products but, rather, afford organometallic complexes resulting from alternate modes of substrate reactivity, such as ring-opening C-O bond cleavage and N-H activation.